Patent GB-880862-A (GB)
Title: Improvements in or relating to the production of coloured photographic images
Inventor: RAMAIX MAURICE ANTOINE DE
IPC: C07D231/46
Filed: 1956-12-31
Abstract: 2 - Phenyl - 3 - methyl - 4 - amino - pyrazolone - 5 is prepared by reducing the corresponding 4-phenylazo derivative with hydrogen and a nickel catalyst.  Similarly, 1-benzoyl-2-phenyl-3-methyl- and 1-phenylsulphonyl-2-phenyl-3-methyl-, 4-phenylazo-5-pyrazolones are reduced to the corresponding 4-amino compounds.  2 - p (a  - hexadecenyl - succinylamido) phenyl - 3-methyl-4-amino-pyrazolone-5 is similarly prepared from the 4-phenylazo compound using palladium as catalyst.  Reduction of 1-phenyl-3 pentadecyl-4-phenylazo-5-pyrazolone with zinc in acetic acid and acetic anhydride gives the 4-diacetylamino derivative.  1 - phenyl - 2 - hexadecyl - 3 - methyl - 4 - amino-5-pyrazolone is prepared by treating 1-phenyl-2-hexadecyl-3-methyl-5-parazolone with sodium nitrite and concentrated hydrochloric acid to give the 4-nitroso compound and reducing this with hydrogen and nickel catalyst. Similarly, 1 - phenyl - 2 - methyl - 3 - pentadecyl -, 1 - phenyl - 2 - methyl - 3 - [m - (a  - hexadecenyl - succinyl - amido) phenyl]-, and the methyl ester of 1-[ - p (succinylamido) phenyl] - 2 - methyl - 3 - pentadecyl-, 5-pyrazolones are converted to the 4-nitroso compounds which are then reduced to the 4-amino compounds (in the latter mentioned case with zinc and hydrochloric acid). 1-Benzoyl-(or 1-phenylsulphonyl) 2-phenyl-3-methyl-4-phenylazo-5-pyrazolone is prepared by adding benzoyl chloride (or benzene sulphonyl chloride) to 2-phenyl-3-methyl-4-phenylazo-5-pyrazolone in the presence of aqueous sodium hydroxide.  1- Phenyl - 2 - hexadecyl - 3 - methyl - 5 - pyrazolone is prepared by fusing 1-phenyl-3-methyl-5-pyrazolone with cetyl-p-toluene sulphonate.  Similarly, 1-phenyl-3-pentadecyl-(or 3-p-nitrophenyl) and in 1-p-nitrophenyl-3-pentadecyl-4-pyrazolones are fused with methyl-p-toluene sulphonate to give the 2-methyl derivatives.  1-Phenyl-2-methyl-3-p-nitrobenzoylamino-5 - pyrazolone is prepared by adding p-nitrobenzoyl chloride and aqueous sodium hydroxide to 1 - phenyl - 2 - methyl - 3 - amino - 5 - pyrazolone. The product is reduced to the 3-p-aminobenzoylamino derivative with H2 and nickel catalyst and then reacted with a -hexadecenyl succinic anhydride to give the 3-[p-(a -hexadecenylsuccinylamido) benzoylamino]-5-pyrazolone.  By reacting this with the diazonium sulphate from p-chloroaniline and reducing with zinc and hydrochloric acid, 1 - phenyl - 2 - methyl - 3 - [p - (a  - hexa - decenylsuccinylamido) benzoylamino] - 4 - amino - 5-pyrazolone is formed.  2-p-nitrophenyl-3-methyl-5-pyrazolone is prepared by adding phosphorus trichloride to a -acetyl-b -(p-nitrophenyl)-hydrazine and acetoacetic acid ethyl ester.  The product is reduced to the 2-p-aminophenyl derivative with H2 and nickel catalyst and then reacted with a -hexadecenyl succinic anhydride to give the 2-[p-(a -hexadecenylsuccinylamido) phenyl]-5 - pyrazolone.  By reacting this with the diazonium sulphate from dichloroaniline, 2-[p-(a -hexadecenylsuccinylamido) phenyl] - 3 - methyl - 4 - dichlorophenylazo - 5-pyrazolone is obtained.  Similarly, 1-phenyl-2-methyl - 3 - p - nitrophenyl - 5 - pyrazolone is reduced with hydrogen and nickel and reacted with a -hexadecenyl succinic anhydride to give 1- phenyl - 2 - methyl - 3 - [p - (a  - hexadecenyl - succinylamido) phenyl] - 5 - pyrazolone; and 1 - p - nitrophenyl-2-methyl-3-pentadecyl-5-pyrazolone is similarly reduced and treated with b -carbomethoxy-propionyl chloride to give 1-[p-(b -carbomethoxy-propionylamino) phenyl]-2-methyl-3-pentadeceyl-5-pyrazolone.  1 - Phenyl - 2 - methyl - 3 - pentadecyl - 4 - carbethoxyamino-5-pyrazolone is prepared by reacting the 4-amino derivative with chloroformic acid ethyl ester. 1- p - nitrophenyl - 3 - pentadecyl - 5 - pyrazolone is prepared by refluxing p-nitrophenyl hydrazine with palmitoyl acetic acid methyl ester in iso propanol.  1 - Phenyl - 3 - pentadecyl - 4 - phenylazo - 5 - pyrazolone is prepared from 1-phenyl-3-pentadecyl-5-pyrazolone and a diazinium salt of aniline.  1 - Phenyl - 2 - (a  - sulphopropyl) - 3 - penta - decyl-4-amino-5-pyrozolone is prepared by treating 1 - phenyl - 3 - pentadecyl - 4 - diacetylamino - 5 - pyrazolone with n-propane sultone and then hydrolysing the acetyl groups.